Imidazole is an organic compound having the formula (CH)2N(NH)CH. Imidazole exists in two equivalent tautomeric forms, with the proton located as either of two nitrogen atoms, this also enables it to function as either an acid or a base. Imidazole is used extensively as a corrosion inhibitor Materials containing or derived from imidazole and members of the imidazole family are useful in a variety of applications including, but not limited to fuel cell catalysts, metal organic frameworks (MOFs), ionic liquids, high temperature polymeric membranes and MOF-derived catalysts.
MOFs are compounds formed from metal ions or clusters and organic molecules (usually rigid) to form one-, two- or three-dimensional porous structures. MOFs are commonly used as gas absorbents, CO2 capture and for hydrogen storage, but may also be used as a starting materials for catalytic materials.
Fuel cells are receiving increasing attention as a viable alternative energy conversion technology. In general, fuel cells directly convert electrochemical energy into electrical energy in an environmentally clean and efficient manner. Fuel cells are contemplated as potential energy sources for everything from small electronics to cars and homes. In order to meet different energy requirements, there are a number of different types of fuel cells in existence today, each with varying chemistries, requirements, operation conditions, and uses.
As one example, Direct Methanol Fuel Cells (DMFCs) rely upon the oxidation of methanol on an electrocatalyst layer to form carbon dioxide. Water is consumed at the anode and produced at the cathode. Positive ions (H+) are transported across a proton exchange membrane to the cathode where they react with oxygen to produce water. Electrons can then be transported via an external circuit from anode to cathode providing power to external sources.
As another example, polymer electrolyte membrane (PEM) fuel cells (also called proton exchange membrane fuel cells) use pure hydrogen (typically supplied by a hydrogen tank) as a fuel. A stream of hydrogen is delivered to the anode side of a membrane-electrode assembly (MEA), where it is catalytically split into protons and electrons. As with the DMFC, the positive ions are transported across a proton exchange membrane to the cathode where they react with oxygen to produce water.
Currently, one of the limiting factors in the wide scale commercialization of PEM and DMFC fuel cells is the cost associated with precious metals. Both DMFC and PEM fuel cells commonly use platinum or platinum alloys as an electrocatalyst. Nobel metals such as platinum are needed to catalyze the sluggish oxygen reduction reaction (ORR) at the cathode. One of the major routes to overcome this limitation is to increase the platinum utilization in noble-metal based electrocatalysts. Another viable route is to use a less expensive, yet still sufficiently active catalyst in larger quantities. Several classes of non-platinum group metals (non-PGM) electrocatalysts have been identified as having adequate oxygen reduction activity to be considered as potential electrocatalysts in commercial fuel cell applications.
Generally, known non-platinum electrocatalysts are supported on high surface area carbon blacks. This is done to increase dispersion, active surface area, and conductivity of the catalytic layer. The synthesis procedure usually includes precipitation of the precursor molecules onto the supporting substrate and pyrolysis of the supported precursor.
Metal-Nitrogen-Carbon (M-N—C) catalysts have been found to be very promising for electrochemical oxygen reduction applications in fuel cell membrane electrode assemblies (MEAs), stacks and fuel cell systems. Critical aspects of the materials include the presence of metallic particles, conjugated carbon-nitrogen-oxide-metallic networks, and nitrogen-bonded carbon. The metallic phase includes metallic, oxide, carbide, nitride, and mixtures of these states. The chemical states and bonding of the M-N—C networks and N—C networks influences performance, for example, increased overall nitrogen content improves ORR performance. However, these systems still suffer from several significant drawbacks including: low stability in acidic environments, low durability in acid and alkaline environments, high costs of nitrogen-carbon precursors and low activity in ORR compared with platinum. The problem of low stability in acid is connected to leaching of metal from carbon-nitrogen network which results in degradation of membrane and ionomer in MEA. Low durability in acid and alkaline solutions is explained by the evolution of significant amount of H2O2 in these environments which is Fenton radical producer resulting in chemical decomposition of ionomer and MEA itself. The low activity is possibly due to the low concentration of active sites in such catalysts due to using external carbon source (medium to high surface carbons like Vulcan, KetjenBlack etc).
Despite the fact that there are several companies working on commercialization of M-N—C catalysts [32-34], the majority of non-PGM catalysts are being synthesized in the researcher's labs in sub-grams amounts. Furthermore, typical synthesis methods usually utilize solvent-based wet impregnation of a carbon support with precursors of a transition metal and a nitrogen-carbon source (complex-forming or chelating agent, polymer precursors or polymers). The estimation of the amount of solvent used for preparation of one kilogram of M-N—C catalysts by the method described is on the order of 200-300 liters, introducing the problem of waste management. In addition to this, some amount of the solvents may stay as a residue during the pyrolysis steps and, thus, contribute to the variability of the synthesis outcome. Furthermore, solvent-based methods necessarily require that the materials used be soluble, preventing the production and development of M-N—C catalysts formed from non-soluble materials.